CN106145180A - A kind of technique that high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process - Google Patents
A kind of technique that high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process Download PDFInfo
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- CN106145180A CN106145180A CN201610487189.0A CN201610487189A CN106145180A CN 106145180 A CN106145180 A CN 106145180A CN 201610487189 A CN201610487189 A CN 201610487189A CN 106145180 A CN106145180 A CN 106145180A
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- fluorine chlorine
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Abstract
nullA kind of technique that high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process of the present invention，The most de-a kind of fluorine and chlorine removal the method utilizing waste acid and zinc oxide fume dust are provided，High-fluorine chlorine zinc oxide is once leached，Leachate uses the waste acid of high-fluorine chlorine，Pressure filter is used to carry out solid-liquor separation after once having leached，Leach filtering residue，After liquid once neutralizes with high-fluorine chlorine zinc oxide again, filter pressing separates，Neutralize slag and return once leaching recovery metal therein，Neutralising fluid adds zinc powder purification and impurity removal，After purification, filter pressing separates，Leach filtering residue，Liquid adds in sodium carbonate secondary and heavy zinc，Secondary separates with rear filter pressing，The liquid that fluorine-containing chlorine is high beats sewage disposal operation，Pulp water containing basic zinc carbonate washes filter pressing，Washing waste liquid beats sewage disposal operation，Slag obtains basic zinc carbonate after drying，The industrial waste product that two kinds are difficult to reclaim by the present invention comprehensively utilizes，Only produce a kind of waste liquid processing the simple high-fluorine chlorine of technical maturity，Remarkable in economical benefits.
Description
Technical field
The invention belongs to nonferrous smelting refuse synthetical recovery processing technology field, particularly relate to a kind of raw at heavy non-ferrous metal
The technique during product, zinc oxide fume dust and the waste acid of output being carried out synthetical recovery process.
Background technology
The sulfuric acid product reclaimed from nonferrous smelting process, typically through gas cleaning, be dried, convert, absorb and tail gas is controlled
The technological processes such as reason.Sulfur trioxide in gas cleaning many employings high energy scrubber washing flue gas of lead-zinc smelting is with a small amount of at present
Flue dust, the waste acid of the heavy metal nonferrous smelting process generations such as lead zinc, acidity about 15%, containing a small amount of heavy metal ion, also simultaneously
Fluorine chloride ion containing higher concentration so that it is be difficult by, it has to use complicated dirty acid treatment process, waste water reaches country
Arranging outside standard, process the waste residue produced and also be difficult to recycling, output part neutralizes slag muck and deposits, and the utilization of waste acid also becomes industry
A difficult problem.Some enterprises use high temperature to concentrate the way improving concentration with removing part fluorine chlorine, and equipment is brought huge by high temperature dilute sulfuric acid
Large impact, some employing membrane processing methods process separating beavy metal, and effect is not ideal enough, and enterprise is also from controlling three oxidation flue gas
Sulfur generates sets about, but does not the most obtain ideal effect, also makes the waste acid of acid manufacturing processes output slowly not utilize, and need to force to process
Waste water reaches outer row.
Iron and steel and Lead-Zinc Sintering Process have the zinc oxide cigarette of the intermediate products of part high-fluorine chlorine zinc oxide, such as steel mill
The ZnO of fuming furnace flue dust of ash, lead smelting, the multiple hearth furnace zinc oxide fume dust of zinc abstraction, fluorine-containing chlorine is the highest, it is impossible to directly return
Receive, it is necessary to could synthetical recovery after de-fluorine and chlorine removal.
Current fluorine and chlorine removal mode mostly is: thorium salt fluorine removal, silica gel fluorine removal, and silver nitride precipitation dechlorinates, and ion exchange dechlorinates,
The modes such as chlorine removal from copper residue, invest relatively large or removal efficiency are low, the most widely used.
Summary of the invention
The sewage that it is an object of the invention to solve the generation of prior art nonferrous heavy metal smelting process is difficult to process and profit
With, the heavy metal smelting processes such as iron and steel and lead zinc to the intermediate products of high-fluorine chlorine zinc oxide process problem, and provide and fill
Point utilize the high-fluorine chlorine zinc oxide fume dust that the high-fluorine chlorine waste acid of metallurgical off-gas acid-making process output and metal smelt process produce
A kind of technique that high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process.
The technical solution adopted in the present invention is:
A kind of technique that high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid carry out synthetical recovery process, comprises the steps:
Step 1), once being leached by high-fluorine chlorine zinc oxide fume dust, leachate uses the waste acid of high-fluorine chlorine.
Step 2), once leached after use pressure filter carry out solid-liquor separation, filtering residue leaches, and is enriched with useful in filtering residue
Heavy metal and a small amount of zinc, it is 4.5-5.0 that remaining liq is once neutralized to pH value with high-fluorine chlorine zinc oxide fume dust again；
After step 3), once neutralization, filter pressing separates, and neutralizes slag and returns once leaching recovery useful heavy metal therein, neutralising fluid
Add zinc powder purification and impurity removal；
After step 4), purification, filter pressing separates, and leaches the filtering residue of cupric cadmium, and remaining liq adds in sodium carbonate secondary and heavy zinc,
Until pH value reaches 6.0-6.5；
Separating with rear filter pressing in step 5), secondary, the waste liquid that fluorine-containing chlorine is high beats sewage disposal operation, the pulp water containing basic zinc carbonate
Washing 1h filter pressing, water lotion beats sewage disposal operation, obtains basic zinc carbonate after filter residue and drying.
Further, the acidity of the described waste acid of step a kind is 150g/l-200g/l, and one time extraction temperature is maintained at 60 DEG C-80
DEG C, the acidity once leaching acid eventually is 30g/l-60g/l, reacts 4h, liquid-solid ratio 5-7:1.
Further, in described step 2, a neutral temperature is maintained at 55 DEG C-75 DEG C, reacts two hours.
Further, in described step 3 during purification and impurity removal, purification temperature is 60 DEG C-75 DEG C, reacts 1.5 hours, zinc
Powder consumption is 2-5 times of the required theoretical amount of reaction, and zinc powder contains zinc more than 98%.
Further, in described step 4, in secondary and heavy zinc during reaction temperature be maintained at 80 DEG C-85 DEG C, reaction
1.5h, carbonate content is more than 98%.
The beneficial effects of the present invention is:
The present invention utilizes and produces in the high-fluorine chlorine waste acid of metallurgical off-gas acid-making process output and iron and steel ferrum and Lead-Zinc Sintering Process
High-fluorine chlorine zinc oxide fume dust output basic carbonate zinc product, the industrial waste product being difficult to reclaim by two kinds comprehensively utilizes,
Only produce a kind of waste liquid processing the simple high-fluorine chlorine of technical maturity, reduce and produce the environmental pollution caused, remarkable in economical benefits.
A kind of technique that high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process that the present invention provides
There are the industrial waste product that high-fluorine chlorine waste acid and high-fluorine chlorine zinc oxide fume dust two kinds are difficult to reclaim and carry out integrated treatment defluorinate chlorine
And reclaim useful products, the advantage only producing a kind of waste liquid processing the simple high-fluorine chlorine of technical maturity.
Accompanying drawing explanation
Fig. 1 a kind of carries out synthetical recovery process to high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid for what the present invention provided
The process structure schematic diagram of technique.
Detailed description of the invention
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1, a kind of technique that high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process, specifically
Comprise the steps:
Step 1: once leached by high-fluorine chlorine zinc oxide fume dust, leachate uses the waste acid of high-fluorine chlorine；Waste acid acidity is
150g/l-200g/l, extraction temperature is maintained at 60 DEG C-80 DEG C, leaches acid 30g/l-60g/l eventually, reacts 4h, liquid-solid ratio 5-7:1；
Step 2: using pressure filter to carry out solid-liquor separation after once having leached, filtering residue leaches, and is enriched with a useful huge sum of money in filtering residue
Belonging to and a small amount of zinc, it is 4.5-5.0 that remaining liq is once neutralized to pH value with high-fluorine chlorine zinc oxide fume dust again, neutral temperature 55
DEG C-75 DEG C, react 2h；
Step 3: after once neutralizing, filter pressing separates, neutralizes slag return once leaching and reclaims useful heavy metal therein, neutralising fluid
Adding zinc powder purification and impurity removal, purification temperature is maintained at 60 DEG C-75 DEG C, response time 1.5h, and zinc powder consumption is the 2-5 of theoretical amount
Times, zinc powder contains zinc more than 98%；
Step 4: after purification, filter pressing separates, and leaches the filtering residue of cupric cadmium, with heavy zinc during after purification, liquid adds sodium carbonate secondary,
Until pH value reaches 6.0-6.5, temperature 80 DEG C-85 DEG C, reacting 1.5h, carbonate content is more than 98%；
Step 5: separate with rear filter pressing in secondary, the waste liquid that fluorine-containing chlorine is high beats sewage disposal operation, the pulp water containing basic zinc carbonate
Washing 1h filter pressing, water lotion beats sewage disposal operation, and slag obtains basic zinc carbonate after drying.
Embodiment 2, a kind of technique that high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process, specifically
Comprise the steps:
Step 1: once leached by high-fluorine chlorine zinc oxide fume dust, leachate uses the waste acid of high-fluorine chlorine；Waste acid acidity is
150g/l-200g/l, extraction temperature is maintained at 70 DEG C, leaches acid 30g/l-60g/l eventually, reacts 4h, liquid-solid ratio 6.5:1；
Step 2: using pressure filter to carry out solid-liquor separation after once having leached, filtering residue leaches, and is enriched with a useful huge sum of money in filtering residue
Belonging to and a small amount of zinc, it is 4.8 that remaining liq is once neutralized to pH value with high-fluorine chlorine zinc oxide fume dust again, neutral temperature 70 DEG C, instead
Answer 2h；
Step 3: after once neutralizing, filter pressing separates, neutralizes slag return once leaching and reclaims useful heavy metal therein, neutralising fluid
Adding zinc powder purification and impurity removal, purification temperature is maintained at 65 DEG C, response time 1.5h, and zinc powder consumption is 4 times of theoretical amount, and zinc powder contains
Zinc more than 98%；
Step 4: after purification, filter pressing separates, and leaches the filtering residue of cupric cadmium, with heavy zinc during after purification, liquid adds sodium carbonate secondary,
Until pH value reaches 6.5, temperature 83 DEG C, reaction 1.5h, carbonate content is more than 98%；
Step 5: separate with rear filter pressing in secondary, the waste liquid that fluorine-containing chlorine is high beats sewage disposal operation, the pulp water containing basic zinc carbonate
Washing 1h filter pressing, water lotion beats sewage disposal operation, and slag obtains basic zinc carbonate after drying.
Embodiment 3, a kind of technique that high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process, specifically
Comprise the steps:
Step 1: once leached by high-fluorine chlorine zinc oxide fume dust, leachate uses the waste acid of high-fluorine chlorine；Waste acid acidity is
150g/l-200g/l, extraction temperature is maintained at 60 DEG C, leaches acid 55g/l eventually, reacts 4h, liquid-solid ratio 7:1；
Step 2: using pressure filter to carry out solid-liquor separation after once having leached, filtering residue leaches, and is enriched with a useful huge sum of money in filtering residue
Belonging to and a small amount of zinc, it is 5.0 that remaining liq is once neutralized to pH value with high-fluorine chlorine zinc oxide fume dust again, neutral temperature 75 DEG C, instead
Answer 2h；
Step 3: after once neutralizing, filter pressing separates, neutralizes slag return once leaching and reclaims useful heavy metal therein, neutralising fluid
Adding zinc powder purification and impurity removal, purification temperature is maintained at 75 DEG C, response time 1.5h, and zinc powder consumption is 2-5 times of theoretical amount, zinc powder
Containing zinc more than 98%；
Step 4: after purification, filter pressing separates, and leaches the filtering residue of cupric cadmium, with heavy zinc during after purification, liquid adds sodium carbonate secondary,
Until pH value reaches 6.5, temperature 85 DEG C, reaction 1.5h, carbonate content is more than 98%；
Step 5: separate with rear filter pressing in secondary, the waste liquid that fluorine-containing chlorine is high beats sewage disposal operation, the pulp water containing basic zinc carbonate
Washing 1h filter pressing, water lotion beats sewage disposal operation, and slag obtains basic zinc carbonate after drying.
By above detailed description of the invention it can be seen that the present invention is a kind of to high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid
The technique carrying out synthetical recovery process has high-fluorine chlorine waste acid and two kinds of Industry Wastes being difficult to reclaim of high-fluorine chlorine zinc oxide fume dust
The product of abandoning carry out integrated treatment defluorinate chlorine and reclaim useful products, only produce a kind of waste liquid processing the simple high-fluorine chlorine of technical maturity
Advantage.
Claims (5)
1. the technique that high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process, it is characterised in that bag
Include following steps:
Step 1), once being leached by high-fluorine chlorine zinc oxide fume dust, leachate uses the waste acid of high-fluorine chlorine.
Step 2), once leached after use pressure filter carry out solid-liquor separation, filtering residue leaches, and is enriched with a useful huge sum of money in filtering residue
Belonging to and a small amount of zinc, it is 4.5-5.0 that remaining liq is once neutralized to pH value with high-fluorine chlorine zinc oxide fume dust again；
After step 3), once neutralization, filter pressing separates, and neutralizes slag and returns once leaching recovery useful heavy metal therein, neutralising fluid
Add zinc powder purification and impurity removal；
After step 4), purification, filter pressing separates, and leaches the filtering residue of cupric cadmium, and remaining liq adds in sodium carbonate secondary and heavy zinc,
Until pH value reaches 6.0-6.5；
Separating with rear filter pressing in step 5), secondary, the waste liquid that fluorine-containing chlorine is high beats sewage disposal operation, the pulp water containing basic zinc carbonate
Washing 1h filter pressing, water lotion beats sewage disposal operation, obtains basic zinc carbonate after filter residue and drying.
The most according to claim 1 a kind of high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process
Technique, it is characterised in that the acidity of the described waste acid of step a kind is 150g/l-200g/l, extraction temperature be maintained at 60 DEG C-
80 DEG C, the acidity once leaching acid eventually is 30g/l-60g/l, reacts 4h, liquid-solid ratio 5-7:1.
The most according to claim 1 a kind of high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process
Technique, it is characterised in that in described step 2, a neutral temperature is maintained at 55 DEG C-75 DEG C, reacts two hours.
The most according to claim 1 a kind of high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process
Technique, it is characterised in that in described step 3 during purification and impurity removal, purification temperature is 60 DEG C-75 DEG C, reacts 1.5 hours,
Zinc powder consumption is 2-5 times of the required theoretical amount of reaction, and zinc powder contains zinc more than 98%.
The most according to claim 1 a kind of high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid are carried out synthetical recovery process
Technique, it is characterised in that in described step 4, in secondary and heavy zinc during reaction temperature be maintained at 80 DEG C-85 DEG C, reaction
1.5h, carbonate content is more than 98%.
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| CN201610487189.0A CN106145180B (en) | 2016-06-29 | 2016-06-29 | A kind of technique that synthetical recovery processing is carried out to high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid |
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| CN201610487189.0A CN106145180B (en) | 2016-06-29 | 2016-06-29 | A kind of technique that synthetical recovery processing is carried out to high-fluorine chlorine zinc oxide fume dust and high-fluorine chlorine waste acid |
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| CN106145180A true CN106145180A (en) | 2016-11-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459166A (en) * | 2017-08-15 | 2017-12-12 | 昆明理工大学 | The curing of sour recycling and arsenic in a kind of waste acid |
| CN112522520A (en) * | 2020-12-02 | 2021-03-19 | 陕西锌业有限公司 | Method for directly producing electrolytic zinc by using secondary zinc oxide |
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| CN101818254A (en) * | 2009-12-23 | 2010-09-01 | 株洲冶炼集团股份有限公司 | Comprehensive recovery method of zinc oxide fume dust |
| CN102286759A (en) * | 2011-07-31 | 2011-12-21 | 红河锌联科技发展有限公司 | Method for preparing electrodeposited zinc from high-fluorine high-chlorine secondary zinc oxide powder |
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2016
- 2016-06-29 CN CN201610487189.0A patent/CN106145180B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101818254A (en) * | 2009-12-23 | 2010-09-01 | 株洲冶炼集团股份有限公司 | Comprehensive recovery method of zinc oxide fume dust |
| CN102286759A (en) * | 2011-07-31 | 2011-12-21 | 红河锌联科技发展有限公司 | Method for preparing electrodeposited zinc from high-fluorine high-chlorine secondary zinc oxide powder |
Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459166A (en) * | 2017-08-15 | 2017-12-12 | 昆明理工大学 | The curing of sour recycling and arsenic in a kind of waste acid |
| CN112522520A (en) * | 2020-12-02 | 2021-03-19 | 陕西锌业有限公司 | Method for directly producing electrolytic zinc by using secondary zinc oxide |
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| CN106145180B (en) | 2018-05-18 |
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